Rylene dyes

ABSTRACT

Rylene dyes of the general formula I  
                 
where the variables are defined as follows: 
         R is hydrogen; optionally substituted C 1 -C 30 -alkyl, C 5 -C 8 -cycloalkyl, aryl or hetaryl;    R′ is bromine; cyano; —NR 3   2 ; optionally substituted aryloxy, arylthio, hetaryloxy or hetarylthio; optionally substituted C 3 -C 18 -alk-1-ynyl; 
 
X, Y are both hydrogen or together are a radical of the formula Ia  
                 
n is 2, 3, 4 or additionally 1 when X and Y are a radical of the formula Ia; n′ is from 1 to 4; m is from 0 to 6.

The present invention relates to novel rylene dyes of the generalformula I

where the variables are defined as follows:

-   -   R is hydrogen;        -   C₁-C₃₀-alkyl whose carbon chain may be interrupted by one or            more —O—, —S—, —NR¹—, —CO— and/or —SO₂— moieties and may be            mono- or polysubstituted by carboxyl, sulfo, hydroxyl,            cyano, C₁-C₆-alkoxy and/or a 5- to 7-membered heterocyclic            radical which is bonded via a nitrogen atom and may contain            further heteroatoms and be aromatic;        -   C₅-C₈-cycloalkyl whose carbon framework may be interrupted            by one or more —O—, —S— and/or —NR¹— moieties and may be            mono- or polysubstituted by C₁-C₆-alkyl;        -   aryl or hetaryl which may each be mono- or polysubstituted            by C₁-C₁₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyl, cyano,            carboxyl, —CONHR², —NHCOR² and/or aryl- or hetarylazo, each            of which may be substituted by C₁-C₁₀-alkyl, C₁-C₆-alkoxy,            halogen, hydroxyl, cyano and/or carboxyl;    -   R′ is bromine; cyano; —NR³ ₂;        -   aryloxy, arylthio, hetaryloxy or hetarylthio, each of which            may be mono- or polysubstituted by C₁-C₁₂-alkyl,            C₁-C₁₂-alkoxy, cyano, —CONHR² and/or —NHCOR²;        -   C₃-C₁₈-alk-1-ynyl whose carbon chain may be interrupted by            one or more —O—, —S—, —NR¹—, —CO— and/or —SO₂— moieties and            may be mono- or polysubstituted by —COOR¹, —SO₃R¹, hydroxyl,            cyano, C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, aryl and/or a 5- to            7-membered heterocyclic radical which is bonded via a            nitrogen atom and may contain further heteroatoms and be            aromatic;    -   R¹ is hydrogen or C₁-C₆-alkyl;    -   R² is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each of which may        be substituted by C₁-C₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyl        and/or cyano;    -   R³ is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each of which may        be substituted by C₁-C₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyl        and/or cyano; both R³ radicals may be joined to give a 5- to        7-membered heterocyclic radical which contains the nitrogen atom        and is bonded via it;    -   X, Y are both hydrogen or bonded together to form a six-membered        ring in a radical of the formula Ia    -   where X is the —NH— group and Y is the other free chemical bond;    -   n is 2, 3, 4 or additionally 1 when X and Y are a radical of the        formula Ia;    -   n′ is from 1 to 4;    -   m is from 0 to 6,

and also to the preparation of the rylene dyes I and to their use forcoloring high molecular weight organic and inorganic materials, inparticular plastics, paints and printing inks, as dispersants, pigmentadditives for organic pigments and intermediates for the preparation ofpigment additives, for producing aqueous polymer dispersions which arecolored or absorb in the near infrared region of the electromagneticspectrum and as a photoconductor in electrophotography.

Aminoanthraquinone-linked rylene vat dyes have been known for some time.DRP 607 341 and U.S. Pat. No. 2,069,663 describe rylene vat dyes basedon naphthalenedicarboximides which color cotton from a red or red-violetvat to blue-green and are prepared from 4-bromonaphthalenedicarboxylicanhydride by subsequent imidation of the anhydridic coupling productwith 1-aminoanthraquinone. However, neither aminoanthraquinone-linkedrylene dyes of the higher homologs of naphthalene nordouble-aminoanthraquinone-linked rylene vat dyes are yet known and,owing to the decreasing solubility with increasing rylene length, therylenedicarboxylic anhydrides can also not be obtained by thepreparative methods described for naphthalenedicarboxylic anhydride.

It is an object of the present invention to provide rylene dyes whichabsorb in the long-wavelength, i.e. in the red and infrared, region ofthe electromagnetic spectrum.

We have found that this object is achieved by the rylene dyes of theformula I defined at the outset.

Preferred rylene dyes can be taken from the subclaim.

A process has also been found for preparing the rylene dyes of theformula I′

where the variables are defined as follows:

-   -   R is hydrogen;        -   C₁-C₃₀-alkyl whose carbon chain may be interrupted by one or            more —O—, —S—, —NR¹—, —CO— and/or —SO₂— moieties and may be            mono- or polysubstituted by carboxyl, sulfo, hydroxyl,            cyano, C₁-C₆-alkoxy and/or a 5- to 7-membered heterocyclic            radical which is bonded via a nitrogen atom and may contain            further heteroatoms and be aromatic;        -   C₅-C₈-cycloalkyl whose carbon framework may be interrupted            by one or more —O—, —S— and/or —NR¹— moieties and may be            mono- or polysubstituted by C₁-C₆-alkyl;        -   aryl or hetaryl which may each be mono- or polysubstituted            by C₁-C₁₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyl, cyano,            carboxyl, —CONHR², —NHCOR² and/or aryl- or hetarylazo, each            of which may be substituted by C₁-C₁₀-alkyl, C₁-C₆-alkoxy,            halogen, hydroxyl, cyano or carboxyl;    -   R′ is bromine; cyano; —NR³ ₂;        -   aryloxy, arylthio, hetaryloxy or hetarylthio, each of which            may be mono- or polysubstituted by C₁-C₁₂-alkyl,            C₁-C₁₂-alkoxy, cyano, —CONHR² and/or —NHCOR²;        -   C₃-C₁₈-alk-1-ynyl whose carbon chain may be interrupted by            one or more —O—, —S—, —NR¹—, —CO— and/or —SO₂— moieties and            may be mono- or polysubstituted by —COOR¹, —SO₃R¹, hydroxyl,            cyano, C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, aryl and/or a 5- to            7-membered heterocyclic radical which is bonded via a            nitrogen atom and may contain further heteroatoms and be            aromatic;    -   R¹ is hydrogen or C₁-C₆-alkyl;    -   R² is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each of which may        be substituted by C₁-C₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyl        or cyano;    -   R³ is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each of which may        be substituted by C₁-C₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyl        and/or cyano; both R³ radicals may be joined to give a 5- to        7-membered heterocyclic radical which contains the nitrogen atom        and is bonded via it;    -   n is 2, 3 or 4;    -   m is from 0 to 6,    -   which comprises    -   a) reacting a rylene derivative monobrominated in the        peri-position of the general formula II′        -   with 1-aminoanthraquinone in a cross-coupling reaction in            the presence of an aprotic organic solvent, of a transition            metal catalyst system and of a base,    -   b) cyclizing the rylenanthramine formed in step a) of the        general formula III′        -   in the presence of a polar organic solvent and of a base to            give the rylene dye of the formula I′ which is unsubstituted            in the rylene core and where m is 0, and    -   c) if desired, converting the rylene dye I′ unsubstituted in the        rylene core and obtained in step b) to the rylene dye of the        formula I′ brominated in the rylene core where R′ is bromine and        m does not equal 0 by reacting with elemental bromine, and    -   d) if desired, converting the rylene dye I′ brominated in the        rylene core and obtained in step c)    -   d1) by reacting with a compound of the general formula IV        -   where Z is sulfur or oxygen and the ring A is an aryl or            hetaryl radical, each of which may be mono- or            polysubstituted by C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy, cyano,            —CONHR² and/or —NHCOR²,        -   in the presence of an inert nitrogen-basic organic solvent            and of a base to give the rylene dye of the formula I′ which            is substituted in the rylene core and where R′ is aryloxy,            arylthio, hetaryloxy or hetarylthio, each of which may be            mono- or polysubstituted by C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy,            cyano, —CONHR² and/or —NHCOR², and m does not equal 0,    -   d2) by reacting with copper(I) cyanide in the presence of a        dipolar aprotic organic solvent to give the rylene dye of the        formula I′ which is substituted in the rylene core and where R′        is cyano and m does not equal 0,    -   d3) by reacting with an alkyne of the general formula V        H—C≡C—R″  V        -   where R″ is a C₁-C₁₆-alkyl radical which may be interrupted            by one or more —O—, —S—, —NR¹—, —CO— and/or —SO₂— moieties            and may be mono- or polysubtituted by —COOR¹, —SO₃R¹,            hydroxyl, cyano, C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, aryl and/or            a 5- to 7-membered heterocyclic radical which is bonded via            a nitrogen atom and may contain further heteroatoms and be            aromatic,        -   in the presence of an aprotic organic solvent, of a            palladium complex as a catalyst, of a copper salt as a            cocatalyst and of a base to give the rylene dye of the            formula I′ which is substituted in the rylene core and where            R′ is —C≡C—R″ and m does not equal 0, or    -   d4) by reacting with ammonia or an amine of the general formula        VI        -   in the presence of a dipolar aprotic organic solvent to give            the rylene dye of the formula I′ which is substituted in the            rylene core and where R′ is —NR³ ₂ and m does not equal 0.

A process has also been found for preparing symmetrical rylene dyes ofthe general formula I″

where the variables R, R′, R¹, R², R³ and m are each as defined for theformula I′ and n is equal to 1, 2, 3 or 4, which comprises

-   -   a) reacting a rylene derivative monobrominated in the        peri-position of the general formula II′        -   with 1,5-diaminoanthraquinone in a double cross-coupling            reaction in the presence of an aprotic organic solvent, of a            transition metal catalyst system and of a base,    -   b) cyclizing the rylenanthramine formed in step a) of the        general formula III″        -   in the presence of a polar organic solvent and of a base to            give the rylene dye of the formula I″ where m is 0, and    -   c) if desired, converting the rylene dye I′ unsubstituted in the        rylene core and obtained in step b) to the rylene dye of the        formula I″ brominated in the rylene core where R′ is bromine and        m is equal to 0 by reacting with elemental bromine and    -   d) if desired, converting the rylene dye I″ brominated in the        rylene core and obtained in step c)    -   d1) by reacting with a compound of the general formula IV        -   where Z is sulfur or oxygen and the ring A is an aryl or            hetaryl radical, each of which may be mono- or            polysubstituted by C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy, cyano,            —CONHR² and/or —NHCOR²,        -   in the presence of an inert nitrogen-basic organic solvent            and of a base to give the rylene dye of the formula I″ which            is substituted in the rylene core and where R′ is aryloxy,            arylthio, hetaryloxy or hetarylthio, each of which may be            mono- or polysubstituted by C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy,            cyano, —CONHR² and/or —NHCOR², and m does not equal 0,    -   d2) by reacting with copper(I) cyanide in the presence of a        dipolar aprotic organic solvent to give the rylene dye of the        formula I″ which is substituted in the rylene core and where R′        is cyano and m does not equal 0,    -   d3) by reacting with an alkyne of the general formula V        H—C≡C—R″  V        -   where R″ is a C₁-C₁₆-alkyl radical which may be interrupted            by one or more —O—, —S—, —NR¹—, —CO— and/or —SO₂— moieties            and may be mono- or polysubstituted by —COOR¹, —SO₃R¹,            hydroxyl, cyano, C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, aryl and/or            a 5- to 7-membered heterocyclic radical which is bonded via            a nitrogen atom and may contain further heteroatoms and be            aromatic,        -   in the presence of an aprotic organic solvent, of a            palladium complex as a catalyst, of a copper salt as a            cocatalyst and of a base to give the rylene dye of the            formula I″ which is substituted in the rylene core and where            R′ is —C≡C—R″ and m does not equal 0, or    -   d4) by reacting with ammonia or an amine of the general formula        VI        -   in the presence of a dipolar aprotic organic solvent to give            the rylene dye of the formula I″ which is substituted in the            rylene core and where R′ is —NR³ ₂ and m does not equal 0.

A process has also been found for preparing nonsymmetrical rylene dyesof the general formula I′″

where the variables R, R′, R¹, R², R³ and m are each as defined for theformula I′, and n and n′ are each equal to 1, 2, 3 or 4, although n≠n′,which comprises

-   -   a1) initially reacting a rylene derivative monobrominated in the        peri-position of the general formula II′        -   with excess 1,5-diaminoanthraquinone in a first            cross-coupling reaction in the presence of an aprotic            organic solvent, of a transition metal catalyst system and            of a base,    -   a2) reacting the aminorylenanthramine obtained in step a) of the        general formula IIIa        -   with a rylene derivative monobrominated in the peri-position            of the general formula II″        -   in the presence of an aprotic organic solvent, of a            transition metal catalyst and of a base in a second            cross-coupling reaction,    -   b) cyclizing the rylenanthramine formed in step a) of the        general formula III′″        -   in the presence of a polar organic solvent and of a base to            give the rylene dye of the formula I′″ which is            unsubstituted in the rylene core and where m is 0, and    -   c) if desired, converting the rylene dye I′″ unsubstituted in        the rylene core and obtained in step b) to the rylene dye of the        formula I′″ brominated in the rylene core where R′ is bromine        and m does not equal 0 by reacting with elemental bromine, and    -   d) if desired, converting the rylene dye I′″ brominated in the        rylene core and obtained in step c)    -   d1) by reacting with a compound of the general formula IV        -   where Z is sulfur or oxygen and the ring A is an aryl or            hetaryl radical, each of which may be mono- or            polysubstituted by C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy, cyano,            —CONHR² and/or —NHCOR²,        -   in the presence of an inert nitrogen-basic organic solvent            and of a base to give the rylene dye of the formula I′″            which is substituted in the rylene core and where R′ is            aryloxy, arylthio, hetaryloxy or hetarylthio, each of which            may be mono- or polysubstituted by C₁-C₁₂-alkyl,            C₁-C₁₂-alkoxy, cyano, —CONHR² and/or —NHCOR², and m does not            equal 0,    -   d2) by reacting with copper(I) cyanide in the presence of a        dipolar aprotic organic solvent to give the rylene dye of the        formula I′″ which is substituted in the rylene core and where R′        is cyano and m does not equal 0,    -   d3) by reacting with an alkyne of the general formula V        H—C≡C—R″  V        -   where R″ is a C₁-C₁₆-alkyl radical which may be interrupted            by one or more —O—, —S—, —NR¹—, —CO— and/or —SO₂— moieties            and may be mono- or polysubstituted by —COOR¹, —SO₃R¹,            hydroxyl, cyano, C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, aryl and/or            a 5- to 7-membered heterocyclic radical which is bonded via            a nitrogen atom and may contain further heteroatoms and be            aromatic,        -   in the presence of an aprotic organic solvent, of a            palladium complex as a catalyst, of a copper salt as a            cocatalyst and of a base to give the rylene dye of the            formula I′″ which is substituted in the rylene core and            where R′ is —C≡C—R″ and m does not equal 0, or    -   d4) by reacting with ammonia or an amine of the general formula        VI        -   in the presence of a dipolar aprotic organic solvent to give            the rylene dye of the formula I′″ which is substituted in            the rylene core and where R′ is —NR³ ₂ and m does not equal            0.

Not least, the applications of the rylene dyes I mentioned at the outsetwere also found.

All alkyl groups occurring in the formulae I to V may be straight-chainor branched. When the alkyl groups are substituted, they generally bear1 or 2 substituents.

The specific examples of suitable R, R¹, R², R³, R′ and R″ radicals (andof their substituents) are as follows:

methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl,isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl,1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl,isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (theabove terms isooctyl, isononyl, isodecyl and isotridecyl are trivialnames and stem from the alcohols obtained by the oxo process);2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl,2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and3-propoxypropyl, 2- und 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl,4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl,4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl,3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 3,6,9,12-tetraoxatridecyl and3,6,9,12-tetraoxatetradecyl;

2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl,2-isopropylthioethyl, 2-butylthioethyl, 2- and 3-methylthiopropyl, 2-and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and3-butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-ethylthiobutyl, 2-and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl,4,8-dithianonyl, 3,7-dithiaoctyl, 3,7-dithianonyl, 2- and4-butylthiobutyl, 4,8-dithiadecyl, 3,6,9-trithiadecyl,3,6,9-trithiaundecyl, 3,6,9-trithiadodecyl, 3,6,9,12-tetrathiatridecyland 3,6,9,12-tetrathiatetradecyl;

2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2- and3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl,6-methyl-3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-diazaoctyl,3,6-dimethyl-3,6-diazaoctyl, 9-methyl-3,6,9-triazadecyl,3,6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl,3,6,9-trimethyl-3,6,9-triazaundecyl, 12-methyl-3,6,9,12-tetraazatridecyland 3,6,9,12-tetramethyl-3,6,9,12-tetraazatridecyl;

propan-2-on-1-yl, butan-3-on-1-yl, butan-3-on-2-yl and2-ethylpentan-3-on-1-yl;

2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl,2-isopropylsulfonylethyl, 2-butylsulfonylethyl, 2- and3-methylsulfonylpropyl, 2- and 3-ethylsulfonylpropyl, 2- and3-propylsulfonylpropyl, 2- and 3-butylsulfonylpropyl, 2- and4-methylsulfonylbutyl, 2- and 4-ethylsulfonylbutyl, 2- and4-propylsulfonylbutyl and 4-butylsulfonylbutyl;

carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl,5-carboxypentyl, 6-carboxyhexyl, 8-carboxyoctyl, 10-carboxydecyl,12-carboxydodecyl and 14-carboxytetradecyl;

sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl,6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl, 12-sulfododecyl and14-sulfotetradecyl;

2-hydroxyethyl, 3-hydroxypropyl, 1-hydroxyprop-2-yl, 2- and4-hydroxybutyl, 1-hydroxybut-2-yl and 8-hydroxy-4-oxaoctyl;

cyanomethyl, 2-cyanoethyl, 3-cyanopropyl,2-methyl-3-ethyl-3-cyanopropyl, 7-cyano-7-ethylheptyl and4,7-dimethyl-7-cyanoheptyl;

methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy,tert-butoxy, pentoxy, isopentoxy, neopentoxy, tert-pentoxy and hexoxy;

carbamoyl, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl,butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl,heptylaminocarbonyl, octylaminocarbonyl, nonylaminocarbonyl,decylaminocarbonyl and phenylaminocarbonyl;

formylamino, acetylamino, propionylamino and benzoylamino;

chlorine, bromine and iodine;

amino, dimethylamino, diethylamino, dipropylamino, dibutylamino,dipentylamino, dihexylamino, diheptylamino, dioctylamino, dinonylamino,didecylamino, N-piperidinyl and N-pyrrolidinyl;

phenylazo, 2-napthylazo, 2-pyridylazo and 2-pyrimidylazo;

phenyl, 2-naphthyl, 2- and 3-pyrryl, 2-, 3- and 4-pyridyl, 2-, 4- and5-pyrimidyl, 3-, 4- and 5-pyrazolyl, 2-, 4- and 5-imidazolyl, 2-, 4- and5-thiazolyl, 3-(1,2,4-triazyl), 2-(1,3,5-triazyl), 6-quinaldyl, 3-, 5-,6- and 8-quinolinyl, 2-benzoxazolyl, 2-benzothiazolyl,5-benzothiadiazolyl, 2- and 5-benzimidazolyl and 1- and 5-isoquinolyl;

2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl,2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl,2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3-and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropylphenyl,2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3,5- and2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl,2,4-, 2,5-, 3,5- and 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-,3- and 4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyland 2,4,6-tri-sec-butylphenyl, 2-, 3- and 4-tert-butylphenyl, 2,4-,2,5-, 3,5- and 2,6-di-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl; 2-,3- and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl,2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4-, 2,5-, 3,5- and2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl,2,4-, 2,5-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl,2,4-, 2,5-, 3,5- and 2,6-diisopropoxyphenyl and 2-, 3- and4-butoxyphenyl; 2-, 3- and 4-chlorophenyl, and 2,4-, 2,5-, 3,5- and2,6-dichlorophenyl; 2-, 3- and 4-hydroxyphenyl and 2,4-, 2,5-, 3,5- and2,6-dihydroxyphenyl; 2-, 3- and 4-cyanophenyl; 3- and 4-carboxyphenyl;3- and 4-carboxamidophenyl, 3- and 4-N-methylcarboxamidophenyl and 3-and 4-N-ethylcarboxamidophenyl; 3- and 4-acetylaminophenyl, 3- and4-propionylaminophenyl and 3- and 4-butyrylaminophenyl; 3- and4-N-phenylaminophenyl, 3- and 4-N-(o-tolyl)aminophenyl, 3- and4-N-(m-tolyl)aminophenyl and 3- and 4-N-(p-tolyl)aminophenyl; 3- and4-(2-pyridyl)aminophenyl, 3- and 4-(3-pyridyl)aminophenyl, 3- and4-(4-pyridyl)aminophenyl, 3- and 4-(2-pyrimidyl)aminophenyl and4-(4-pyrimidyl)aminophenyl;

4-phenylazophenyl, 4-(1-naphthylazo)phenyl, 4-(2-naphthylazo)-phenyl,4-(4-naphthylazo)phenyl, 4-(2-pyridylazo)phenyl, 4-(3-pyridylazo)phenyl,4-(4-pyridylazo)phenyl, 4-(2-pyrimidylazo)phenyl,4-(4-pyrimidylazo)phenyl and 4-(5-pyrimidylazo)-phenyl;

cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl,cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl,3- and 4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and4-tert-butylcyclohexyl, cycloheptyl, 2-, 3- and 4-methylcycloheptyl, 2-,3- and 4-ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and4-isopropylcycloheptyl, 3- and 4-butylcycloheptyl, 3- and4-sec-butylcycloheptyl, 3- and 4-tert-butylcycloheptyl, cyclooctyl, 2-,3-, 4- and 5-methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclooctyl, 3-, 4-and 5-propylcyclooctyl, 2-dioxanyl, 4-morpholinyl, 2- and3-tetrahydrofuryl, 1-, 2- and 3-pyrrolidinyl and 1-, 2-, 3- and4-piperidyl;

phenoxy, phenylthio, 2-naphthyloxy, 2-naphthylthio, 2-, 3- and4-pyridyloxy, 2-, 3- and 4-pyridylthio, 2-, 4- and 5-pyrimidyloxy and2-, 4- and 5-pyrimidylthio.

Examples of particularly preferred R′ radicals are bromine and alsop-tert-butylphenoxy, p-(1,1-dimethylpropyl)phenoxy,p-(1,1-dimethylbutyl)phenoxy, p-(1,1-dimethylpentyl)phenoxy,p-(1,1,3,3-tetramethylbutyl)phenoxy,p-(2-cyclopentyl-1,1-dimethylethyl)phenoxy,p-(2-cyclohexyl-1,1-dimethylethyl)phenoxy,p-(2-cycloheptyl-1,1-dimethylethyl)phenoxy andp-(1,1-dimethyl-2-(4-morpholinyl)ethyl)phenoxy.

The rylene dyes I (I′, I″ and I′″) can advantageously be prepared by themultistage processes according to the invention starting from the rylenederivative II′ monobrominated in the peri-position.

To prepare the rylene dyes I′ in step a), II′ is reacted with1-aminoanthraquinone in a cross-coupling reaction to give therylenanthramine III′ or, to prepare the symmetrical rylene dyes I″, with1,5-diaminoanthraquinone to give the rylenanthramine III″. In thepreparation of the nonsymmetrical rylene dyes III′″, step a) is carriedout in two stages by initially reacting the monobrominated rylenederivative II′ with excess 1,5-diaminoanthraquinone (step a1)) andreacting the resultant aminorylenanthramine IIIa with anothermonobrominated rylene derivative II″ to give the rylenanthramine III′″(step a2)).

The rylenanthramines III′, III″ and III′″ (summarized hereinbelow asrylenanthramines III) are subsequently subjected in step b) to acyclization to give the rylene dyes I unsubstituted in the rylene core(m=0).

Rylene dyes I brominated in the rylene core (R′═Br, m≠0) can be obtainedin a subsequent step c) by reaction with elemental bromine.

The further rylene dyes I substituted in the rylene core are obtainablefrom the brominated rylene dyes I by bromine exchange in step d). Forinstance, rylene dyes I which are substituted by (het)aryloxy and(het)arylthio, cyano, alkynyl radicals R′ or amino radicals R′ can beprepared by reaction with a (het)aromatic (thio)alcohol IV (step d1)),copper(I) cyanide (step d2)), a 1-alkyne V (step d3)) or ammonia or aprimary or secondary amine VI (step d4).

The naphthalene-1,8- or perylene-3,4-di-carboxamides monobrominated inthe peri-position which are used as reactants in step a) are disclosedby WO-A-01/16109. The terrylene- or quaterrylene-3,4-dicarboxamidesmonobrominated in the peri-position which are used as reactants aredisclosed by DE-A-101 08 156, unpublished at the priority date of thepresent invention, and can be prepared by the following three-stageprocess described there:

-   -   A) alkaline hydrolysis, on one side, of an asymmetric        rylenetetracarboxylic diimide of the formula VII        -   where R⁴ is C₅-C₈-cycloalkyl whose carbon framework may be            interrupted by one or more —O—, —S— and/or —NR²— moieties            and which may be mono- or polysubstituted by C₁-C₆-alkyl,            and n is 2 or 3,        -   in the presence of a polar organic solvent,    -   B) decarboxylation, on one side, of the rylenetetracarboxylic        monoimide monoanhydride formed in step A) of the formula VIII        -   in the presence of a tertiary nitrogen-basic compound and of            a transition metal catalyst and    -   C) reaction of the rylene-3,4-dicarboximide unsubstituted in the        20 peri-position of the formula IX        -   with elemental bromine.

Polar solvents suitable for step A) of this process are in particularbranched C₃-C₆-alcohols, such as isopropanol, tert-butanol and2-methyl-2-butanol.

In general, from 40 to 200 g of solvent are used per gram of VII.

Suitable bases are inorganic bases, in particular alkali metal andalkaline earth metal hydroxides, e.g. sodium hydroxide and potassiumhydroxide, which are preferably used in the form of aqueous solutions orsuspensions (generally from 50 to 80% by weight), and organic bases, inparticular alkali metal and alkaline earth metal alkoxides, althoughpreference is given to using sodium alkoxides and potassium alkoxides,such as sodium methoxide, potassium methoxide, potassium isopropoxideand potassium tert-butoxide, which are typically used in anhydrous form.

In general, from 5 to 50 equivalents of base, based on VII, arerequired.

The reaction temperature is generally from 50 to 120° C., preferablyfrom 60 to 100° C.

The hydrolysis is complete typically within from 10 to 40 h.

In step B) of this process, the rylenetetracarboxylic monoimidemonoanhydrides VIII are decarboxylated on one side in the presence of atertiary nitrogen-basic compound as a solvent and of a transition metalcatalyst.

Suitable solvents are in particular high-boiling nitrogen bases, forexample cyclic amides such as N-methylpyrrolidone, and aromaticheterocycles such as quinoline, isoquinoline and quinaldine.

Typical amounts of solvent are from 20 to 150 g per gram of VII.

Suitable catalysts are in particular the transition metals copper andzinc and also particularly their inorganic and organic salts which arepreferably used in anhydrous form.

Examples of preferred salts are copper(I) oxide, copper(II) oxide,copper(I) chloride, copper(II) acetate, zinc acetate and zincpropionate, and particular preference is given to copper(I) oxide andzinc acetate.

It will be appreciated that mixtures of the catalysts mentioned can alsobe used.

In general, from 50 to 90 mol % of catalyst is used, based on VIII.

The reaction temperature is generally from 100 to 250° C., in particularfrom 160 to 200° C. It is recommended to work with the use of aprotective gas atmosphere (for example nitrogen).

Typically, the decarboxylation is complete within from 3 to 20 h.

Step C) of this process, the regioselective bromination of therylene-3,4-dicarboximide IX, is preferably carried out in an aliphaticmonocarboxylic acid, in particular a C₁-C₄-carboxylic acid, such asformic acid, acetic acid, propionic acid, butyric acid or mixturesthereof, or in a halogenated, aliphatic or aromatic solvent, such asmethylene chloride, chloroform or chlorobenzene.

Typically, from 5 to 30 g, preferably from 15 to 25 g, of solvent areused per gram of IX to be brominated.

In general, the presence of a halogenation catalyst is not required.However, if acceleration of the bromination reaction is desired (by afactor from about 1.5 to 2), it is recommended to add elemental iodine,preferably in an amount of from 1 to 5 mol %, based on IX.

In general, the molar ratio of bromine to IX is from about 1:1 to 5:1,preferably from 3:1 to 4:1.

The reaction temperature is from 0 to 70° C., in particular from 10 to40° C.

Depending on the reactivity of the substrate IX and the presence orabsence of iodine, the bromination is complete typically within from 2to 12 h.

Step a) of the processes according to the invention, the cross-couplingof the rylene derivatives II′ with 1-aminoanthraquinone or1,5-diaminoanthraquinone, is carried out in the presence of an aproticorganic solvent, of a transition metal catalyst system and of a base.

Particularly suitable aprotic organic solvents are anhydrous inertaromatic solvents such as benzene and its alkylation products, forexample toluene and o-, m- and p-xylene, and also aliphatic andcycloaliphatic ethers such as dimethoxyethane, 1,4-dioxane andtetrahydrofuran.

The amount of solvent is typically from 60 to 380 g, preferably from 120to 150 g, per gram of II′.

Suitable transition metal catalysts are in particular palladiumcompounds, and preferred examples are palladium(0) and palladium(II)complexes, such as tris(dibenzylidenacetone)-dipalladium(0),dichloro[1,1′-bis(diphenylphosphino)ferrocene]-palladium(II) anddichloro(1,5-cyclooctadiene)palladium(II), and palladium(II) acetate.

Typically, the transition metal catalyst is used in an amount of from0.4 to 5 mol %, in particular from 1 to 3 mol %, based on II′.

Preference is given to additionally using a cocatalyst based onphosphine. Preferred examples of this cocatalyst are bidentate phosphineligands, such as racemic 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,1′-bis(diphenylphosphino)ferrocene,1,1′-bis-(di-o-tolylphosphino)ferrocene,1,1′-bis(di-p-methoxyphenylphosphino)ferrocene and2,2′-bis(di-o-tolylphosphino)diphenyl ether, and phosphines acting asmonodentate phosphine ligands, such as tri-o-tolylphosphine,tri-tert-butylphosphine and triphenylphosphine.

Suitable amounts of cocatalyst are generally from 1 to 10 mol %,preferably from 1 to 5 mol %, based on II′.

Particularly suitable bases are alkali metal amides, in particularalkali metal di(C₃-C₆-alkyl)amides, and alkali metal alkoxides, inparticular the alkali metal salts of secondary and tertiary aliphatic(C₃-C₆—)alcohols. Preferred examples of these bases are: lithiumdiisopropylamide, sodium diisopropylamide and potassiumdiisopropylamide, and also lithium isopropoxide, sodium isopropoxide,potassium isopropoxide, lithium tert-butoxide, sodium tert-butoxide andpotassium tert-butoxide, and particular preference is given to sodiumtert-butoxide and potassium tert-butoxide.

In general, an at least equimolar amount of base, preferably 1.1 mol ofbase per mole of II′, is used.

For the preparation of the rylene dyes I′, 1-aminoanthraquinone andrylene derivative II′ are generally used in a molar ratio of from 0.8:1to 1:1. For the preparation of the symmetrical rylene dyes I″, aparticularly suitable molar ratio of 1,5-diaminoanthraquinone to rylenederivative II′ is generally from 0.4:1 to 0.5:1.

The reaction temperature is typically from 50 to 120° C., preferablyfrom 70 to 100° C.

It is recommended to work under a protective gas atmosphere.

Depending on the reactivity of the rylene derivatives II′ and the amountof catalyst used, the reaction time is generally from 6 to 40 h, inparticualr from 18 to 24 h.

In the preparation of the nonsymmetrical rylene dyes I′″, the procedurein the partial steps a1) and a2) is in each case similar to step a). Instep a1), only the molar ratio of 1,5-diaminoanthraquinone to rylenederivative II′ is adjusted, preferably to from 1:0.3 to 1:0.8, and,similarly to step a), the molar ratio of aminorylenanthramine IIIa torylene derivative II″ in step a2) is from 0.8:1 to 1:1.

In terms of method, the procedure in the steps a) is advantageously asfollows:

solvent, catalyst and cocatalyst are initially charged in a protectivegas atmosphere, the rylene derivative II′ or II″, 1-aminoanthraquinoneor 1,5-diaminoanthraquinone or aminorylenanthramine IIIa and base areadded in succession with stirring and the mixture is heated underprotective gas to the desired reaction temperature for from 6 to 24 h.After cooling to room temperature, the solid constituents are filteredout of the reaction mixture, washed with a polar organic solvent, forexample ethanol, and subsequently with water. If desired, the filteredmaterial can additionally be stirred in a dilute mineral acid, forexample in sulfuric acid, and finally washed to neutrality with water.

The purification of the rylenanthramines III prepared in this way isgenerally sufficient for further processing. Optionally, the crudeproduct can be further purified by reprecipitation from chloroform,methylene chloride/petroleum ether or N-methylpyrrolidone, or by columnchromatography on silica gel using a methylene chloride/tetrahydrofuranmixture as the eluent.

Step b) of the processes according to the invention, the cyclization ofthe rylenanthramines III to give the rylene dyes I unsubstituted in therylene core, is carried out in the presence of a polar organic solventand of a base.

Suitable for this purpose are in particular high-boiling, oxygen ornitrogen solvents, for example ethers such as diphenyl ether, diethyleneglycol dimethyl and diethyl ether, polyhydric alcohols such asdiethylene glycol, amino alcohols such as aminoethanol, carboxamidessuch as dimethylformamide and dimethylacetamide, N-methylpyrrolidone andtertiary nitrogen bases such as 1,5-diazabicyclo[4.3.0]non-3-ene and1,8-diazabicyclo[5.4.0]undec-7-ene.

In general, from 10 to 50 g, preferably from 20 to 30 g, of solvent areused per gram of III.

Suitable bases are inorganic bases, in particular alkali metal andalkaline earth metal hydroxides, such as sodium hydroxide and potassiumhydroxide, and alkali metal and alkaline earth metal carbonates, such assodium carbonate, potassium carbonate and cesium carbonate, and alsoorganic bases, in particular alkali metal and alkaline earth metalalkoxides, and preference is given to sodium alkoxides and potassiumalkoxides, such as sodium methoxide, potassium methoxide, potassiumisopropoxide and potassium tert-butoxide, and alkali metal amides, suchas lithium diisopropylamide, sodium diisopropylamide and potassiumdiisopropylamide, which are typically used in anhydrous form.

In general, from 3 to 30, in particular from 8 to 10, molar equivalentsof base, based on III, are used.

The reaction temperature is typically from 50 to 180° C., preferablyfrom 90 to 120° C.

It is advantageous to work under a protective gas atmosphere.

Depending on the reactivity of the rylenanthramines III, the reactiontime is generally from 2 to 80 h.

In terms of method, the procedure in step b) is advantageously asfollows:

anhydrous solvent and base are initially charged in a protective gasatmosphere, the mixture is heated to the desired reaction temperature,and the rylenanthramine III, if desired in the form of a solution orsuspension in very little further solvent, is added. After a reactiontime of from 2 to 80 h, the reaction mixture is cooled to 50-60° C., andan amount of low-boiling alcohol, e.g. methanol or ethanol, equivalentto the volume of solvent is added, and the mixture is allowed to coolwith stirring. Subsequently, the pH is adjusted to 6 by adding an acid,for example 50% by weight acetic acid, and the reaction product isfiltered off, washed with hot water and dried under reduced pressure atabout 100° C.

If desired, the unsubstituted rylene dyes I obtained can be furtherpurified by extraction with a solvent such as tetrahydrofuran.

5 When rylene dyes I (I′, I″ or I′″) are to be prepared which arebrominated in the rylene core, the unsubstituted rylene dyes I of stepc) of the processes according to the invention are reacted withelemental bromine.

Suitable solvents are in particular aliphatic monocarboxylic acids whichpreferably have from 1 to 4 carbon atoms, such as formic acid, aceticacid, propionic acid and butyric acid, and also mixtures thereof, andhalogenated aliphatic or aromatic hydrocarbons, such as methylenechloride, chloroform and chlorobenzene.

Typically, from 50 to 300 g, preferably from 70 to 100 g, of solvent areused per gram of rylene dye I to be brominated.

The molar ratio of bromine to rylene dye I depends on the desired degreeof bromination. In general, for each bromine atom to be introduced, from1.1 to 3 mol of I are used.

In general, the presence of a halogenation catalyst is not required.However, if acceleration of the bromination reaction is desired (by afactor of from about 1.5 to 3), it is recommended to add elementaliodine, preferably in an amount of from 1 to 5 mol %, based on I.

The reaction temperature is generally from 0 to 70° C., preferably from10 to 40° C.

Depending on the reactivity of the rylene dye I to be brominated and thepresence or absence of iodine, the bromination is complete typicallywithin from 2 to 24 h.

In terms of method, the procedure in step c) is advantageously asfollows:

the solvent and rylene dye I are initially charged and the mixture isadjusted to the desired reaction temperature with stirring within from15 to 30 min, any catalyst and subsequently, within from 5 to 10 min,the desired amount of bromine are added and the mixture is stirred withthe exclusion of light at the reaction temperature for from 2 to 24 h.After excess bromine is removed using a vigorous nitrogen stream, thereaction mixture is introduced into about the same amount of analiphatic alcohol, such as methanol, and stirred overnight, theprecipitated product is filtered off, washed preferably with the samealcohol and with water, and dried under reduced pressure at about 120°C.

Typically, the brominated rylene dyes I prepared in this way arepurified before subsequent reactions by column chromatography on silicagel using chloroform as the eluent or by extraction with a solvent, suchas ethanol.

Rylene dyes I which are substituted in the rylene core by optionallyalkyl- or alkoxy-substituted aryloxy, arylthio, hetaryloxy orhetarylthio can be prepared in step d1) of the processes according tothe invention by reaction of the brominated rylene dyes I with anaromatic or heteroaromatic alcohol or thioalcohol IV in the presence ofan inert nitrogen-basic organic solvent and of a base.

Suitable inert nitrogen-basic solvents for this purpose are especiallypolar solvents, in particular nitrogen heterocycles, such as pyridine,pyrimidine, quinoline, isoquinoline, quinaldine and preferablyN-methylpyrrolidone, and also carboxamides such as N,N-dimethylformamideand N,N-dimethylacetamide.

Depending on the solubility of the brominated rylene dye I, the amountof solvent is typically from 2 to 40 g, preferably from 4 to 25 g, pergram of brominated rylene dye I.

Suitable bases are in particular nonnucleophilic or only weaklynucleophilic compounds. Examples of such bases are alkali metalhydroxides such as potassium hydroxide and sodium hydroxide, alkalimetal carbonates such as potassium carbonate and sodium carbonate, andalso alkali metal alkoxides of tertiary alcohols, such as lithiumtert-butoxide, sodium tert-butoxide and potassium tert-butoxide, whichare used in anhydrous form.

In general, from 0.8 to 1.5, preferably from 1 to 1.2, molar equivalentsof base are used per mole of bromine atom to be substituted.

The molar ratio of brominated rylene dye I to alcohol or thioalcohol IVlikewise depends on the number of bromine atoms to be substituted. Ingeneral, from 1 to 2 mol, preferably from 1 to 1.3 mol, of IV are usedper mole of bromine atom to be exchanged.

The reaction temperature is typically in the range from 50 to 200° C.,preferably from 60 to 140° C.

It is recommended to carry out the reaction under protective gas.

Depending on the reactivity of the brominated rylene dye I, the reactiontime is from about 2 to 48 h.

Selection of the reaction conditions—amount of alcohol or thioalcohol IVand base and also reaction temperature—can advantageously be used tocontrol the bromine exchange, so that not only rylene dyes I in whichall bromine atoms have been exchanged but also rylene dyes I which stillcontain bromine can be prepared without any problems. If desired, thebromine can subsequently be removed from the rylene dye I.

In terms of method, the procedure in step d1) is advantageously that thesolvent is initially charged, brominated rylene dye I, alcohol orthioalcohol IV and base are added, and the solution or suspensionobtained is heated with stirring under protective gas to the desiredreaction temperature for from 2 to 48 h.

The reaction product can be isolated after cooling to room temperatureby directly filtering off the precipitated reaction product or byfiltering off after diluting with 3-4 times the volume of water, of adilute inorganic acid, for example from 5 to 10% by weight hydrochloricacid, or of an aliphatic alcohol, for example methanol, washinginitially with a little solvent and subsequently with water until thewashings are neutral and drying under reduced pressure.

In many cases, it may be advantageous for the achievement of a highproduct purity to carry out the reaction in two stages. In this case,the brominated rylene dye I is reacted initially with only a partialamount, advantageously the amount required to exchange the most labilebromine substituents, of alcohol or thioalcohol IV and base, the partlyconverted product is removed from the reaction mixture by filtration andsubsequently reacted with the remaining amount of IV and base to givethe desired product.

Rylene dyes I which are substituted by cyano in the rylene core can beprepared by step d2) of the processes according to the invention byreacting the brominated rylene dyes I with copper(I) cyanide in thepresence of a dipolar aprotic organic solvent.

Suitable dipolar aprotic solvents are in particular sulfoxides such asdimethyl sulfoxide, sulfones, such as sulfolane, N-methylpyrrolidone,carboxamides such as dimethylformamide and dimethylacetamide, andnitrogen heterocycles such as pyridine, pyrimidine, quinoline,isoquinoline and quinaldine.

The amount of solvent is in itself uncritical, and typically from 20 to100 g, preferably from 40 to 60 g, of solvent are used per gram ofbrominated rylene dye I.

The molar ratio of brominated rylene dye I to copper(I) cyanide dependson the number of bromine atoms to be substituted. In general, from 1 to3 mol, preferably from 1 to 1.3 mol, of copper(I) cyanide are used permole of bromine atom to be exchanged.

The reaction temperature is typically from 50 to 280° C., in particularfrom 100 to 180° C.

Advantageously, the reaction is carried out under protective gas.

The reaction time is generally from about 1 to 48 h.

In terms of method, the procedure in step d2) is advantageously that thesolvent is initially charged, brominated rylene dye I and copper(I)cyanide are added and the solution or suspension obtained is heated withstirring under protective gas to the desired reaction temperature forfrom 1 to 48 h.

The reaction product can be isolated as in step d1).

Rylene dyes I which are substituted in the rylene core by optionallysubstituted C₃-C₁₈-1-alkynyl are obtainable in step d3) of the processesaccording to the invention by reacting the brominated rylene dyes I withan alkyne V in the presence of an aprotic solvent, of a palladiumcomplex as a catalyst, of a copper salt as a cocatalyst and of a base.

Suitable aprotic solvents are in particular linear and cyclic aliphaticethers having up to 10 carbon atoms, such as diethyl ether, di-n-propylether, di-n-butyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane,dioxane and in particular tetrahydrofuran.

In general, from 20 to 100 g, preferably from 40 to 60 g, of solvent areused per gram of brominated rylene dye I.

The base added serves simultaneously as a cosolvent. Suitable for thispurpose are in particular organic nitrogen bases miscible with theethers and having a melting point below room temperature and a boilingpoint above the reaction temperature. Preferred bases are aliphaticamines having up to 15 carbon atoms, in particular tertiary amines, suchas triethylamine, tri-n-propylamine and tri-n-butylamine, andcycloaliphatic amines, in particular piperidine.

Typically, from 0.2 to 1.5 g, preferably from 0.8 to 1.2 g of base areused per gram of solvent.

Examples of palladium complexes suitable as catalyst aretetrakis(tris-o-tolylphosphine)palladium(0),[1,2-bis(diphenyl-phosphino)ethane]palladium(II) chloride,[1,1′-bis(diphylphosphino)ferrocene]palladium(II) chloride,bis(triethylphosphine)palladium(II) chloride,bis(tricyclohexylphosphine)-palladium(II) chloride,bis(triphenylphosphine)palladium(II) acetate,(2,2′-bipyridyl)palladium(II) chloride and in particulartetrakis(triphenylphosphine)palladium(0),bis(triphenylphosphine)palladium(II) chloride,bis(acetonitrile)palladium(II) chloride andbis(benzonitrile)palladium(II) chloride.

An example of a copper(I) salt particularly suitable as a cocatalyst iscopper(I) iodide.

In general, from 2 to 15 mol %, preferably from 5 to 10 mol %, ofpalladium complex, and generally from 2 to 20 mol %, preferably from 7to 12 mol %, of copper salt, based in each case on brominated rylene dyeI, is used.

The molar ratio of brominated rylene dye I to alkyne depends in turn onthe number of bromine atoms to be substituted. In general, from 1 to 2mol, preferably from 1 to 1.5 mol, of alkyne V are used per mole ofbromine atom to be exchanged.

The reaction tempereature is typically from 20 to 140° C., in particularfrom 40 to 90° C.

Depending on the alkyne used, the reaction can be carried out atatmospheric pressure or at an increased pressure of typically up to 50bar. The method under pressure is required when volatile alkynes areused.

The reaction time is typically from 3 to 12 h.

In terms of method, the procedure in step d3) is advantageously that thesubstantially anhydrous solvent and substantially anhydrous base areinitially charged, brominated rylene dye I is added, then after repeateddegassing and aeration with dry nitrogen, copper salt, palladium complexand alkyne (volatile alkynes are injected into the closed apparatusafter weighing) are added with stirring under nitrogen to the solutionor suspension obtained and heated to the desired reaction temperaturefor from 3 to 12 h.

The reaction product can be isolated as in step d1).

Rylene dyes I which are substituted in the rylene core by —NR³ ₂ can beprepared in step d4) of the processes according to the invention byreacting the brominated rylene dyes I with ammonia or an amine VI in thepresence of a dipolar aprotic organic solvent.

Suitable dipolar aprotic solvents are the solvents already mentioned byway of example for step d2).

The amount of solvent is in itself uncritical, and typically from 20 to100 g, preferably from 40 to 60 g, of solvent are used per gram ofbrominated rylene dye I.

The molar ratio of brominated rylene dye I to ammonia or amine VIdepends in turn on the number of bromine atoms to be substituted. Ingeneral, from 1 to 4 mol, preferably from 1 to 1.5 mol, of ammonia oramine VI are used per mole of bromine atom to be exchanged.

The reaction temperature is typically from 50 to 280° C., in particularfrom 80 to 160° C.

Depending on the amine VI used, the reaction can be carried out atatmospheric pressure or at an increased pressure of generally up to 50bar. The method under pressure is required when ammonia or volatileamines VI are used.

In general, the substituted rylene dyes I obtained according to theinvention already have such a high purity (>95%) that furtherpurification can be dispensed with. Analytically pure products can beobtained by recrystallization from aromatic solvents such as toluene andxylene, or halogenated aliphatic or aromatic hydrocarbons such asmethylene chloride and chloroform or chlorobenzene and1,2-dichlorobenzene, or by filtration of a solution of the products inthese solvents through silica gel and subsequent concentration.

The rylene dyes I according to the invention have outstandingsuitability for homogeneous coloring of high molecular weight organicand inorganic materials, especially, for example, of plastics, inparticular thermoplastics, paints and printing inks, and also oxidiclayer systems.

They are also suitable as dispersants, pigment additives for organicpigments and intermediates for the preparation of pigment additives, forproducing aqueous polymer dispersions which are colored or absorb in thenear infrared region of the electromagnetic spectrum and asphotoconductors in electrophotography.

EXAMPLES PREPARATION OF RYLENE DYES OF THE FORMULAE I′, I″ AND I′″ACCORDING TO THE INVENTION a1) Preparation of Rylenanthramines III′Examples 1 to 5

A mixture of x₁ g (9.0 mmol) of peri-bromorylene-3,4-dicarboximide II′,1.8 g (8.0 mmol) of 1-aminoanthraquinone, 60 mg (0.27 mmol) ofpalladium(II) acetate, 0.39 g (0.71 mmol) ofbis(2-diphenylphosphinophenyl) ether and a₁ 1 of anhydrous toluene wasadmixed under nitrogen with 0.96 g (10.0 mmol) of sodium tert-butoxideand then heated to 80° C.

After t₂ h, the reaction mixture was cooled to room temperature.

The reaction product was filtered off, washed initially with 250 ml oftoluene, then with 500 ml of ethanol and finally with hot water anddried under reduced pressure at 80° C.

Further details on the experiments and also their results are compiledin table 1. TABLE 1 x₁ peri-Bromorylene-3,4-dicarboximide a₁ t₁ Yieldm.p. Ex. [g] II′ [l] [h] [g]/[%] Appearance [° C.] 1 5.09-Bromo-N-(2,6-diisopropylphenyl)- 0.7 14 5.7/90 gold-black, >350perylene-3,4-dicarboximide amorphous 2 6.211-Bromo-N-dodecylterrylene-3,4-dicarboximide 1.0 24 6.4/85black-violet, >350 amorphous 3 5.7 11-Bromo-N-(4-methoxyphenyl)- 1.0 246.3/90 black-violet, >350 terrylene-3,4-dicarboximide amorphous 4 6.211-Bromo-N-(2,6-diisopropylphenyl)- 1.0 24 6.8/91 black-violet, >350terrylene-3,4-dicarboximide microcrystalline 5 7.313-Bromo-N-(2,6-diisopropylphenyl)- 1.5 40 6.8/80 green-black, >350quaterrylene-3,4-dicarboximide crystalline

Analytical Data for Example 1N-(2,6-Diisopropylphenyl)-9-[N′-1-(aminoanthraquinonyl)]-perylene-3,4-dicarboximide

Elemental analysis (% by wt. calc./found): C, 82.0/81.9; H, 4.9/4.9; N,4.0/3.9; O, 9.1/9.0;

Mass (FD, 8 kV): m/z=702.2 (M⁺, 100%);

IR (KBr): ν (cm⁻¹)=1697, 1662, 1629, 1592, 1563;

UV/VIS (CHCl₃): λ_(max) (ε)=530 (28 400) nm.

Analytical Data for Example 2N-Dodecyl-9-[N′-1-(aminoanthraquinonyl)]perylene-3,4-dicarboximide

Elemental analysis (% by wt. calc./found): C, 81.1/81.0; H, 6.0/5.9; N,3.9/4.0; O, 9.0/9.1;

Mass (FD, 8 kV): m/z=710.3 (M⁺, 100%).

Analytical Data for Example 3N-(4-Methoxyphenyl)-9-[N′-1-(aminoanthraquinonyl)]-perylene-3,4-dicarboximide

Elemental analysis (% by wt. calc./found): C, 79.6/79.6; H, 3.7/3.6; N,4.3/4.4; O, 12.3/12.3;

Mass (FD, 8 kV): m/z=648.2 (M⁺, 100%).

Analytical Data for Example 4N-(2,6-Diisopropylphenyl)-11-[N′-1-(aminoanthraquinonyl)]-terrylene-3,4-dicarboximide

Elemental analysis (% by wt. calc./found): C, 84.2/84.0; H, 4.6/4.8; N,3.4/3.6; O, 7.7/7.5;

Mass (FD, 8 kV): m/z=826.3 (M⁺, 100%).

Analytical Data for Example 5N-(2,6-Diisopropylphenyl)-13-[N′-1-(aminoanthraquinonyl)]-quaterrylene-3,4-dicarboximide

Elemental analysis (% by wt. calc./found): C, 85.9/86.0; H, 4.5/4.3; N,3.0/3.2; O, 6.7/6.4;

Mass (FD, 8 kV): m/z=950.3 (M⁺, 100%).

a2) Preparation of Rylenanthramines III″ Examples 6 to 11

A mixture of x₂ g (9.0 mmol) of peri-bromorylene-3,4-dicarboximide II′,0.95 g (4.0 mmol) of 1,5-diaminoanthraquinone, 60 mg (0.27 mmol) ofpalladium(II) acetate, 0.39 g (0.71 mmol) ofbis(2-diphenylphosphinophenyl)ether and a₂ 1 of anhydrous toluene wasadmixed under nitrogen with 0.96 g (10.0 mmol) of sodium tert-butoxideand then heated to 80° C. After t₂ h, the reaction mixture was cooled toroom temperature.

The reaction product was filtered off, washed initially with 250 ml oftoluene, then with 500 ml of ethanol and finally with hot water anddried under reduced pressure at 80° C.

Further details on the experiments and also their results are compiledin table 2. The yield is based on II″. TABLE 2 x₂peri-Bromorylene-3,4-dicarboximide a₂ t₂ Yield m.p. Ex. [g] II′ [l] [h][g]/[%] Appearance [° C.] 6 4.0 4-Bromo-N-(2,6-diisopropylphenyl)- 0.424 4.0/94 dark brown, 245 naphthalene-1,8-dicarboximide amorphous 7 5.09-Bromo-N-(2,6-diisopropylphenyl)- 0.5 18 5.0/92 black-violet, 290perylene-3,4-dicarboximide microcrystalline 8 6.211-Bromo-N-dodecylterrylene- 1.0 24 5.5/84 black, >350 3,4-dicarboximideamorphous 9 5.7 11-Bromo-N-(4-methoxyphenyl)- 1.0 24 5.2/86black-violet, >350 terrylene-3,4-dicarboximide amorphous 10 6.211-Bromo-N-(2,6-diisopropylphenyl)- 1.0 30 6.1/93 black-violet, >350terrylene-3,4-dicarboximide amorphous 11 7.313-Bromo-N-(2,6-diisopropylphenyl)- 2.0 40 6.7/88 black, >350quaterrylene-3,4-dicarboximide microcrystalline

Analytical Data for Example 6N,N′-Bis[4-(N″-(2,6-diisopropylphenyl)naphthalene-1,8-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 78.5/78.7; H, 5.5/5.3; N,5.9/5.8; O, 10.1/10.0;

Mass (FD, 8 kV): m/z=948.4 (M⁺, 100%);

IR (KBr): ν (cm⁻¹)=1706, 1668, 1629, 1571;

UV/VIS (CHCl₃): λ_(max) (ε)=426 (18 400), 531 (13 200) nm.

Analytical Data for Example 7N,N′-Bis[9-(N″-(2,6-diisopropylphenyl)perylene-3,4-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 82.3/82.0; H, 5.1/5.3; N,4.7/4.7; O, 8.0/8.0;

Mass (FD, 8 kV): m/z=1196.5 (M⁺, 100%);

IR (KBr): ν (cm⁻¹)=1702, 1662, 1627, 1594, 1565;

UV/VIS (CHCl₃): λ_(max) (ε)=556 (27 100) nm.

Analytical Data for Example 8N,N′-Bis[9-(N″-dodecylperylene-3,4-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 81.2/81.0; H, 6.3/6.3; N,4.6/4.7; O, 7.9/7.9;

Mass (FD, 8 kV): m/z=1212.6 (M⁺, 100%).

Analytical Data for Example 9N,N′-Bis[9-(N″-(4-methoxyphenyl)perylene-3,4-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 79.4/79.5; H, 3.7/3.5; N,5.1/5.0; O, 11.8/11.9;

Mass (FD, 8 kV): m/z=1088.3 (M⁺, 100%).

Analytical Data for Example 10N,N′-Bis[11-(N″-(2,6-diisopropylphenyl)terrylene-3,4-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 84.7/84.5; H, 4.7/4.8; N,3.9/3.9; O, 6.6/6.7;

Mass (FD, 8 kV): m/z=1444.5 (M⁺, 100%);

IR (KBr): ν (cm⁻¹)=1700, 1669, 1635, 1565.

Analytical Data for Example 11N,N′-Bis[13-(N″-(2,6-diisopropylphenyl)quaterrylene-3,4-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 86.5/86.5; H, 4.5/4.3; N,3.3/3.4; O, 5.7/5.7;

Mass (FD, 8 kV): m/z=1692.6 (M⁺, 100%);

IR (KBr): ν (cm⁻¹)=1708, 1666, 1627, 1566.

a3) Preparation of Rylenanthramines III′″ Example 12

Step a′):

A mixture of 3.3 g (7.5 mmol) ofN-(2,6-diisopropylphenyl)-4-bromonaphthalene-1,8-dicarboximide (II′),2.4 g (10.0 mmol) of 1,5-diaminoanthraquinone, 60 mg (0.27 mmol) ofpalladium(II) acetate, 0.39 g (0.71 mmol) ofbis(2-diphenylphosphinophenyl)ether and 500 ml of anhydrous toluene wasadmixed under nitrogen with 0.77 g (8.0 mmol) of sodium tert-butoxideand then heated to 80° C. After 20 h, the reaction mixture was cooled toroom temperature.

The crude product was filtered off, washed initially with 100 ml oftoluene, then with 300 ml of ethanol and finally with hot water, anddried under reduced pressure at 80° C. Column chromatography on silicagel using chloroform as the eluent provided pureN-[4-(N′-(2,6-diisopropylphenyl)-naphthalene-1,8-dicarboximid)yl]-1,5-diaminoanthraquinone.

Step a″):

A mixture of 5.0 g (9.0 mmol) of9-bromo-N-(2,6-diisopropyl-phenyl)perylene-3,4-dicarboximide (II′″), 4.5g (7.5 mmol) ofN-[4-(N′-(2,6-diisopropylphenyl)naphthalene-1,8-dicarboximid)yl]-1,5-diaminoanthraquinone,60 mg (0.27 mmol) of palladium(II) acetate, 0.39 g (0.71 mmol) ofbis(2-diphenylphosphinophenyl)ether and 1 1 of anhydrous toluene wasadmixed under nitrogen with 0.96 g (10.0 mmol) of sodium tert-butoxideand then heated to 80° C. After 24 h, the reaction mixture was cooled toroom temperature.

The reaction product was filtered off, washed initially with 150 ml oftoluene, then with 500 ml of ethanol and finally with hot water, anddried under reduced pressure at 80° C.

5.6 g of rylenanthramine III′″ were obtained, which corresponds to ayield of 52%, based on 1,5-diaminoanthraquinone.

Analytical Data for Example 12N-[4-(N″-(2,6-Diisopropylphenyl)naphthalene-1,8-dicarboximid)yl]-N′-[9-(N′″-(2,6-diisopropylphenyl)perylene-3,4-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 80.6/80.4; H, 5.3/5.4; N,5.2/5.4; O, 8.9/8.7;

Mass (FD, 8 kV): m/z=1073.3 (M⁺, 100%);

IR (KBr): ν (cm⁻¹)=1704, 1669, 1631, 1568;

UV/VIS (CHCl₃): λ_(max)=433, 561 nm.

b) Preparation of Unsubstituted Rylene Dyes I′, I″ and I′″ Examples 13to 24

A mixture of 15.0 g (133 mmol) of potassium tert-butoxide, 20.0 g (131mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene and 200 ml of diethyleneglycol diethyl ether was stirred under nitrogen at 120° C. for 1 h.After adding X₃ g (10.0 mmol) of rylenanthramine III′, III″ or III′″suspended in 100 ml of anhydrous N-methylpyrrolidone, the mixture washeated to T₃° C. and kept at this temperature for t₃ h.

After cooling to 50° C. and adding 300 ml of methanol, the reactionmixture was cooled to room temperature. Sufficient 50% by weight aceticacid was then added to set a pH of 6. The crude product was filteredoff, washed with hot water until the washings were neutral, dried at100° C. under reduced pressure and subsequently purified by Soxhlettextraction using tetrahydrofuran.

Further details on these experiments and also their results are compiledin table 3. TABLE 3 x₃ Rylenanthraquinone T₃ t₃ Yield m.p. Ex. [g] imideIII from ex. [° C.] [h] [g]/[%] Appearance [° C.] 13 7.0 1 130 2 6.4/92blue-green, amorphous >350 14 8.4 2 140 12 6.8/82 violet-black,amorphous >350 15 7.7 3 140 6 6.0/78 black, amorphous >350 16 8.3 4 1408 6.9/84 blue-black, amorphous >350 17 9.5 5 130 6 6.1/64 black,amorphous >350 18 9.5 6 125 12 6.8/72 green, amorphous >350 19 12.0 7130 24 6.3/53 violet-black, amorphous >350 20 14.6 8 160 40 9.2/63black, amorphous >350 21 13.3 9 160 12 7.6/57 black, amorphous >350 2214.5 10 160 12 9.8/68 black, amorphous >350 23 16.9 11 160 48 8.8/52black, amorphous >350 24 10.7 12 140 36 6.4/60 blue-black, amorphous>350

Analytical Data for Example 13 Cyclodehydrogenation product ofN-(2,6-diisopropylphenyl)-9-[N′-1-(aminoanthraquinonyl)]perylene-3,4-dicarboximide

Elemental analysis (% by wt. calc./found): C, 82.3/82.1; H, 4.6/4.8; N,4.0/4.0; O, 9.1/9.0;

Mass (FD, 8 kV): m/z=700.2 (M⁺, 100%);

UV/VIS (1,2,4-trichlorobenzene): λ_(max) (ε)=601 (23 200), 800 (22 000)nm.

Analytical Data for Example 14 Cyclodehydrogenation product ofN-dodecyl-9-[N′-1-(aminoanthraquinonyl)]perylene-3,4-dicarboximide

Elemental analysis (% by wt. calc./found): C, 81.3/81.3; H, 5.7/5.8; N,4.0/3.9; O, 9.0/8.9;

Mass (FD, 8 kV): m/z=708.3 (M⁺, 100%);

UV/VIS (1,2,4-trichlorobenzene): λ_(max) (ε)=602 (23 100), 802 (22 000)nm.

Analytical Data for Example 15 Cyclodehydrogenation product ofN-(4-methoxyphenyl)-9-[N′-1-(aminoanthraquinonyl)]perylene-3,4-dicarboximide

Elemental analysis (% by wt. calc./found): C, 79.9/79.8; H, 3.4/3.4; N,4.3/4.4; O, 12.4/12.3;

Mass (FD, 8 kV): m/z=646.2 (M⁺, 100%);

UV/VIS (1,2,4-trichlorobenzene): λ_(max) (ε)=602 (23 100), 801 (21 900)nm.

Analytical Data for Example 16 Cyclodehydrogenation product ofN-(2,6-diisopropylphenyl)-11-[N′-1-(aminoanthraquinonyl)]terrylene-3,4-dicarboximide

Elemental analysis (% by wt. calc./found): C, 84.5/84.7; H, 4.4/4.4; N,3.4/3.2; O, 7.8/7.6;

Mass (FD, 8 kV): m/z=824.9 (M⁺, 100%).

Analytical Data for Example 17 Cyclodehydrogenation product ofN-(2,6-diisopropylphenyl)-13-[N′-1-(aminoanthraquinonyl)]quaterrylene-3,4-dicarboximide

Elemental analysis (% by wt. calc./found): C, 86.1/86.0; H, 4.3/4.4; N,3.0/3.2; O, 6.7/6.4;

Mass (FD, 8 kV): m/z=948.3 (M⁺, 100%).

Analytical Data for Example 18 Cyclodehydrogenation product ofN,N′-bis[4-(N″-(2,6-diisopropylphenyl)naphthalene-1,8-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 78.8/78.5; H, 5.1/5.3; N,5.9/5.9; O, 10.2/10.2;

Mass (FD, 8 kV): m/z=944.4 (M⁺, 100%);

IR (KBr): ν (cm⁻¹)=1697, 1654, 1621;

UV/VIS (1,2,4-trichlorobenzene): λ_(max) (ε)=440 (15 800), 735 (16 000),778 (15 900) nm.

Analytical Data for Example 19 Cyclodehydrogenation product ofN,N′-bis[9-(N″-(2,6-diisopropylphenyl)perylene-3,4-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 82.5/82.2; H, 4.7/4.8; N,4.7/4.7; O, 8.0/7.8;

Mass (FD, 8 kV): m/z=1192.4 (M⁺, 100%).

Analytical Data for Example 20 Cyclodehydrogenation product ofN,N′-bis[9-(N″-dodecylperylene-3,4-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 81.4/81.4; H, 6.0/5.9; N,4.6/4.5; O, 7.9/8.0;

Mass (FD, 8 kV): m/z=1208.6 (M⁺, 100%).

Analytical Data for Example 21 Cyclodehydrogenation product ofN,N′-bis[9-(N″-(4-methoxyphenyl)perylene-3,4-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 79.7/79.6; H, 3.3/3.4; N,5.2/5.0; O, 11.8/11.9;

Mass (FD, 8 kV): m/z=1084.3 (M⁺, 100%).

Analytical Data for Example 22 Cyclodehydrogenation product ofN,N′-bis[11-(N″-(2,6-diisopropylphenyl)terrylene-3,4-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 85.0/85.1; H, 4.5/4.3; N,3.9/3.9; O, 6.7/6.7;

Mass (FD, 8 kV): m/z=1445.7 (M⁺, 100%).

Analytical Data for Example 23 Cyclodehydrogenation product ofN,N′-bis[13-(N″-(2,6-diisopropylphenyl)quaterrylene-3,4-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 86.7/86.6; H, 4.3/4.3; N,3.3/3.3; O, 5.7/5.7;

Mass (FD, 8 kV): m/z=1688.6 (M⁺, 100%).

Analytical Data for Example 24 Cyclodehydrogenation product ofN-[4-(N″-(2,6-diisopropylphenyl)naphthalene-1,8-dicarboximid)yl]-N′-[9-(N′″-(2,6-diisopropylphenyl)perylene-3,4-dicarboximid)yl]-1,5-diaminoanthraquinone

Elemental analysis (% by wt. calc./found): C, 80.9/80.8; H, 4.9/5.0; N,5.2/5.3; O, 9.0/8.8;

Mass (FD, 8 kV): m/z=1068.4 (M⁺, 100%).

c) Preparation of Brominated Rylene Dyes I′ and I″ Examples 25 and 26

x₄ g (10 mmol) of the unsubstituted rylene dye I′ or I″ were suspendedin 0.5 1 of chlorobenzene for 30 min. After adding 0.1 g (0.44 mmol) ofiodine and y₄ g (b₄ mol) of bromine, the mixture was stirred with theexclusion of light at 50° C. for 16 h.

After the reaction had been ended, excess bromine was removed from thereaction mixture by passing through a vigorous nitrogen stream. Afterdiluting the mixture with 1 1 of methanol, the mixture was stirred atroom temperature overnight. The precipitated product was filtered off,washed initially with 0.5 1 of methanol and then with water until thewashings were neutral and dried at 120° C. under reduced pressue. Thecrude product was purified by a column filtration on silica gel usingchloroform as the eluent.

Further details on these experiments and also their results are compiledin table 4. The degree of bromination is quoted as the number m ofbromine atoms per molecule of rylene dye. TABLE 4 Rylene x₄ dye I y₄ b₄Yield m.p. Ex. [g] from ex. [g] [mol] m [g]/[%] Appearance [° C.] 25 7.013 10.0 0.10 2 7.6/89 blue-green, >350 amorphous 26 11.9 19 16.0 0.10 49.7/64 violet-black, >350 amorphous

Analytical Data for Example 25

Elemental analysis (% by wt. calc./found): C, 67.2/67.1; H, 3.5/3.6; N,3.3/3.1; O, 7.5/7.3; Br, 18.6/18.9;

Mass (FD, 8 kV): m/z=856.1 (M⁺, 100%).

Analytical Data for Example 26

Elemental analysis (% by wt. calc/found): C, 65.3/65.1; H, 3.5/3.5; N,3.7/3.5; O, 6.4/6.5; Br, 21.2/21.5;

Masse (FD, 8 kV): m/z=1504.1 (M⁺, 100%).

d1) Preparation of a di-cyano-substituted Rylene Dye I′ Example 27

8.58 g (10 mmol) of the dibrominated rylene dye I′ from example 25 and3.00 g (36 mmol) of copper(I) cyanide were suspended under nitrogen in0.2 1 of sulfolane for 30 min. The mixture was then heated to 285° C.for 2 h.

After the reaction had been ended and 0.5 1 of methanol had been added,the precipitate was removed. The residue was heated with 15 g ofiron(III) chloride hexahydrate, 150 ml of water and 36 ml of conc.hydrochloric acid to 70° C. for 1 h. After cooling, the precipitate wasremoved, washed with water and dried at 120° C. under reduced pressure.

7.23 g of the rylene dye I′ were obtained as a violet powder. The crudeproduct was purified by column filtration through silica gel usingchloroform as the eluent to remove insoluble constituents.

Analytical Data for Example 27

Elemental analysis (% by wt. calc./found): C, 78.0/77.9; H, 4.0/4.1; N,7.5/7.4; O, 8.5/8.5;

Mass (FD, 8 kV): m/z=750.2 (M⁺, 100%).

d2) Preparation of a di-hexynyl-substituted Rylene Dye I′ Example 28

4.29 g (5 mmol) of the dibrominated rylene dye I′ from example 25 wereintroduced in a nitrogen countercurrent with stirring into a mixture of200 ml of freshly distilled piperidine and 200 ml of tetrahydrofuran.After successive addition of 90 mg (0.46 mmol) of copper(I) iodide, 450mg (0.38 mmol) of tetrakis(triphenylphosphine)palladium(0) and 1.016 g(12 mmol) of 1-hexyne, the mixture was heated under nitrogen to 80° C.for 10 h.

After cooling to room temperature, the resultant black reaction mixturewas introduced with stirring into 1.2 1 of semiconcentrated hydrochloricacid. The precipitated reaction product was washed initially with 0.5 1of semiconcentrated hydrochloric acid, then washed to neutrality withwater and dried at 100° C. under reduced pressure. The crude product waspurified chromatographically on silica gel using chloroform as theeluent.

2.19 g of the rylene dye I′ in the form of a black-violet powder wereobtained, which corresponds to a yield of 51%.

Analytical Data for Example 28

Elemental analysis (% by wt. calc./found): C, 83.7/83.4; H, 5.62/5.75;N, 3.25/3.33; O, 7.43/7.52;

Mass (FD, 8 kV): m/z=860.4 (M⁺, 100%).

3) Preparation of phenoxy-substituted Rylene Dyes I′, I″ and I′″Examples 29 and 30

A mixture of x₅ g (10 mmol) of the brominated rylene dye I, y₅ g (b₅mmol) of tert-octylphenol, z₅ g (c₅ mmol) of potassium carbonate and 300ml of N-methylpyrrolidone were heated with stirring under nitrogen to85° C. for t₅ h.

After cooling to room temperature and adding 500 ml of methanol, thereaction product was filtered off, washed with water until the washingswere neutral and subsequently dried at 80° C. under reduced pressure. Toremove insoluble constituents, a column filtration was carried out onsilica gel using dichloromethane as the eluent.

Further details on these experiments and also their results are compiledin table 5. m is the number of phenoxy susbstituents per molecule ofrylene dye. TABLE 5 y₅ [g] z₅ [g] x₅ Brominated rylene b₅ c₅ t₅ Yieldm.p. Ex. [g] dye I from ex. [mmol] [mmol] [h] m [g]/[%] Appearance [°C.] 29 8.6 25 4.522 3.324 8 2  9.1/82 violet-black, >350 amorphous 3015.1 26 9.144 6.648 16 4 14.1/70 black, amorphous >350

Analytical Data for Example 30

Elemental analysis (% by wt. calc./found): C, 67.2/67.1; H, 3.5/3.6; N,3.3/3.1; O, 7.5/7.3; Br, 18.6/18.9;

Mass (FD, 8 kV): m/z=856.1 (M⁺, 100%).

Analytical Data for Example 31

Elemental analysis (% by wt. calc./found): C, 65.3/65.1; H, 3.5/3.5; N,3.7/3.5; O, 6.4/6.5; Br, 21.2/21.5;

Mass (FD, 8 kV): m/z=1504.1 (M⁺, 100%).

1. A rylene dye of the general formula I

where the variables are defined as follows: R is hydrogen; C₁-C₃₀-alkylwhose carbon chain may be interrupted by one or more —O—, —S—, —NR¹—,—CO— and/or —SO₂— moieties and may be mono- or polysubstituted bycarboxyl, sulfo, hydroxyl, cyano, C₁-C₆-alkoxy and/or a 5- to 7-memberedheterocyclic radical which is bonded via a nitrogen atom and may containfurther heteroatoms and be aromatic; C₅-C₈-cycloalkyl whose carbonframework may be interrupted by one or more —O—, —S— and/or —NR¹—moieties and may be mono- or polysubstituted by C₁-C₆-alkyl; aryl orhetaryl which may each be mono- or polysubstituted by C₁-C₁₈-alkyl,C₁-C₆-alkoxy, halogen, hydroxyl, cyano, carboxyl, —CONHR², —NHCOR²and/or aryl- or hetarylazo, each of which may be substituted byC₁-C₁₀-alkyl, C₁-C₆-alkoxy, halogen, hydroxyl, cyano and/or carboxyl; R′is bromine; cyano; —NR³ ₂; aryloxy, arylthio, hetaryloxy or hetarylthio,each of which may be mono- or polysubstituted by C₁-C₁₂-alkyl,C₁-C₁₂-alkoxy, cyano, —CONHR² and/or —NHCOR²; C₃-C₁₈-alk-1-ynyl whosecarbon chain may be interrupted by one or more —O—, —S—, —NR¹—, —CO—and/or —SO₂— moieties and may be mono- or polysubstituted by —COOR¹,—SO₃R¹, hydroxyl, cyano, C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, aryl and/or a5- to 7-membered heterocyclic radical which is bonded via a nitrogenatom and may contain further heteroatoms and be aromatic; R¹ is hydrogenor C₁-C₆-alkyl; R² is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each ofwhich may be substituted by C₁-C₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyland/or cyano; R³ is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each ofwhich may be substituted by C₁-C₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyland/or cyano; both R³ radicals may be joined to give a 5- to 7-memberedheterocyclic radical which contains the nitrogen atom and is bonded viait; X, Y are both hydrogen or bonded together to form a six-memberedring in a radical of the formula Ia

where X is the —NH— group and Y is the other free chemical bond; n is 2,3, 4 or additionally 1 when X and Y are a radical of the formula Ia; n′is from 1 to 4; m is from 0 to
 6. 2. A rylene dye of the formula I asclaimed in claim 1, where the variables are defined as follows: R isC₁-C₃₀-alkyl whose carbon chain may be interrupted by one or more —O—,—S—, —NR¹—, —CO— and/or —SO₂— moieties and may be mono- orpolysubstituted by hydroxyl, cyano, C₁-C₆-alkoxy and/or a 5- to7-membered heterocyclic radical which is bonded via a nitrogen atom andmay contain further heteroatoms and be aromatic; aryl or hetaryl whichmay each be mono- or polysubstituted by C₁-C₁₈-alkyl, C₁-C₆-alkoxy,hydroxyl, cyano, —CONHR² and/or —NHCOR²; R′ is bromine or aryloxy whichmay be mono- or polysubstituted by C₁-C₁₂-alkyl, C₁-C₆-alkoxy and/orcyano; R¹ is hydrogen or C₁-C₆-alkyl; R² is hydrogen; C₁-C₁₈-alkyl; arylor hetaryl, each of which may be substituted by C₁-C₈-alkyl,C₁-C₆-alkoxy and/or cyano; X, Y are both hydrogen or bonded together toform a six-membered ring in a radical of the formula Ia

where X is the —NH— group and Y is the other free chemical bond; n is 2,3, 4 or additionally 1 when X and Y are a radical of the formula Ia; n′is from 1 to 4; m is from 0 to
 6. 3. A process for preparing rylene dyesof the general formula I′

where the variables are defined as follows: R is hydrogen; C₁-C₃₀-alkylwhose carbon chain may be interrupted by one or more —O—, —S—, —NR¹—,—CO— and/or —SO₂— moieties and may be mono- or polysubstituted bycarboxyl, sulfo, hydroxyl, cyano, C₁-C₆-alkoxy and/or a 5- to 7-memberedheterocyclic radical which is bonded via a nitrogen atom and may containfurther heteroatoms and be aromatic; C₅-C₈-cycloalkyl whose carbonframework may be interrupted by one or more —O—, —S— and/or —NR¹—moieties and may be mono- or polysubstituted by C₁-C₆-alkyl; aryl orhetaryl which may each be mono- or polysubstituted by C₁-C₁₈-alkyl,C₁-C₆-alkoxy, halogen, hydroxyl, cyano, carboxyl, —CONHR², —NHCOR²and/or aryl- or hetarylazo, each of which may be substituted byC₁-C₁₀-alkyl, C₁-C₆-alkoxy, halogen, hydroxyl, cyano or carboxyl; R′ isbromine; cyano; —NR³ ₂; aryloxy, arylthio, hetaryloxy or hetarylthio,each of which may be mono- or polysubstituted by C₁-C₁₂-alkyl,C₁-C₁₂-alkoxy, cyano, —CONHR² and/or —NHCOR²; C₃-C₁₈-alk-1-ynyl whosecarbon chain may be interrupted by one or more —O—, —S—, —NR¹—, —CO—and/or —SO₂— moieties and may be mono- or polysubstituted by —COOR¹,—SO₃R¹, hydroxyl, cyano, C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, aryl and/or a5- to 7-membered heterocyclic radical which is bonded via a nitrogenatom and may contain further heteroatoms and be aromatic; R¹ is hydrogenor C₁-C₆-alkyl; R² is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each ofwhich may be substituted by C₁-C₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxylor cyano; R³ is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each of whichmay be substituted by C₁-C₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyland/or cyano; both R³ radicals may be joined to give a 5- to 7-memberedheterocyclic radical which contains the nitrogen atom and is bonded viait; n is2,3or4; m is from 0 to 6, which comprises a) reacting a rylenederivative monobrominated in the peri-position of the general formulaII′

with 1-aminoanthraquinone in a cross-coupling reaction in the presenceof an aprotic organic solvent, of a transition metal catalyst system andof a base, b) cyclizing the rylenanthramine formed in step a) of thegeneral formula III′

in the presence of a polar organic solvent and of a base to give therylene dye of the formula I′ which is unsubstituted in the rylene coreand where m is 0, and c) if desired, converting the rylene dye I′unsubstituted in the rylene core and obtained in step b) to the rylenedye of the formula I′ brominated in the rylene core where R′ is bromineand m does not equal 0 by reacting with elemental bromine, and d) ifdesired, converting the rylene dye I′ brominated in the rylene core andobtained in step c) d1) by reacting with a compound of the generalformula IV

where Z is sulfur or oxygen and the ring A is an aryl or hetarylradical, each of which may be mono- or polysubstituted by C₁-C₁₂-alkyl,C₁-C₁₂-alkoxy, cyano, —CONHR² and/or —NHCOR², in the presence of aninert nitrogen-basic organic solvent and of a base to give the rylenedye of the formula I′ which is substituted in the rylene core and whereR′ is aryloxy, arylthio, hetaryloxy or hetarylthio, each of which may bemono- or polysubstituted by C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy, cyano, —CONHR²and/or —NHCOR², and m does not equal 0, d2) by reacting with copper(I)cyanide in the presence of a dipolar aprotic organic solvent to give therylene dye of the formula I′ which is substituted in the rylene core andwhere R′ is cyano and m does not equal 0, d3) by reacting with an alkyneof the general formula VH—C≡C—R″  V where R″ is a C₁-C₁₆-alkyl radical which may be interruptedby one or more —O—, —S—, —NR¹—, —CO— and/or —SO₂— moieties and may bemono- or polysubstituted by —COOR¹, —SO₃R¹, hydroxyl, cyano,C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, aryl and/or a 5- to 7-memberedheterocyclic radical which is bonded via a nitrogen atom and may containfurther heteroatoms and be aromatic, in the presence of an aproticorganic solvent, of a palladium complex as a catalyst, of a copper saltas a cocatalyst and of a base to give the rylene dye of the formula I′which is substituted in the rylene core and where R′ is —C≡C—R″ and mdoes not equal 0, or d4) by reacting with ammonia or an amine of thegeneral formula VI

in the presence of a dipolar aprotic organic solvent to give the rylenedye of the formula I′ which is substituted in the rylene core and whereR′ is —NR³ ₂ and m does not equal
 0. 4. A process for preparingsymmetrical rylene dyes of the general formula I″

where the variables are defined as follows: R is hydrogen; C₁-C₃₀-alkylwhose carbon chain may be interrupted by one or more —O—, —S—, —NR¹—,—CO— and/or —SO₂— moieties and may be mono- or polysubstituted bycarboxyl, sulfo, hydroxyl, cyano, C₁-C₆-alkoxy and/or a 5- to 7-memberedheterocyclic radical which is bonded via a nitrogen atom and may containfurther heteroatoms and be aromatic; C₅-C₈-cycloalkyl whose carbonframework may be interrupted by one or more —O—, —S— and/or —NR¹—moieties and may be mono- or polysubstituted by C₁-C₆-alkyl; aryl orhetaryl which may each be mono- or polysubstituted by C₁-C₁₈-alkyl,C₁-C₆-alkoxy, halogen, hydroxyl, cyano, carboxyl, —CONHR², —NHCOR²and/or aryl- or hetarylazo, each of which may be substituted byC₁-C₁₀-alkyl, C₁-C₆-alkoxy, halogen, hydroxyl, cyano and/or carboxyl; R′is bromine; cyano; —NR³ ₂; aryloxy, arylthio, hetaryloxy or hetarylthio,each of which may be mono- or polysubstituted by C₁-C₁₂-alkyl,C₁-C₁₂-alkoxy, cyano, —CONHR₂ and/or —NHCOR²; C₃-C₁₈-alk-1-ynyl whosecarbon chain may be interrupted by one or more —O—, —S—, —NR¹—, —CO—and/or —SO₂— moieties and may be mono- or polysubstituted by —COOR¹,—SO₃R¹, hydroxyl, cyano, C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, aryl and/or a5- to 7-membered heterocyclic radical which is bonded via a nitrogenatom and may contain further heteroatoms and be aromatic; R¹ is hydrogenor C₁-C₆-alkyl; R² is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each ofwhich may be substituted by C₁-C₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyland/or cyano; R³ is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each ofwhich may be substituted by C₁-C₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyland/or cyano; both R³ radicals may be joined to give a 5- to 7-memberedheterocyclic radical which contains the nitrogen atom and is bonded viait; n is 1,2,3 or4; m is from 0 to 6, which comprises a) reacting arylene derivative monobrominated in the peri-position of the generalformula II′

with 1,5-diaminoanthraquinone in a double cross-coupling reaction in thepresence of an aprotic organic solvent, of a transition metal catalystsystem and of a base, b) cyclizing the rylenanthramine formed in step a)of the general formula III″

in the presence of a polar organic solvent and of a base to give therylene dye of the formula I″ where m is 0, and c) if desired, convertingthe rylene dye I′ unsubstituted in the rylene core and obtained in stepb) to the rylene dye of the formula I″ brominated in the rylene corewhere R′ is bromine and m is equal to 0 by reacting with elementalbromine, and d) if desired, converting the rylene dye I″ brominated inthe rylene core and obtained in step c) d1) by reacting with a compoundof the general formula IV

where Z is sulfur or oxygen and the ring A is an aryl or hetarylradical, each of which may be mono- or polysubstituted by C₁-C₁₂-alkyl,C₁-C₁₂-alkoxy, cyano, —CONHR² and/or —NHCOR², in the presence of aninert nitrogen-basic organic solvent and of a base to give the rylenedye of the formula I″ which is substituted in the rylene core and whereR′ is aryloxy, arylthio, hetaryloxy or hetarylthio, each of which may bemono- or polysubstituted by C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy, cyano, —CONHR²and/or —NHCOR², and m does not equal 0, d2) by reacting with copper(I)cyanide in the presence of a dipolar aprotic organic solvent to give therylene dye of the formula I″ which is substituted in the rylene core andwhere R′ is cyano and m does not equal 0, d3) by reacting with an alkyneof the general formula VH—C≡C—R″  V where R″ is a C₁-C₁₆-alkyl radical which may be interruptedby one or more —O—, —S—, —NR¹—, —CO— and/or —SO₂— moieties and may bemono- or polysubtituted by —COOR¹, —SO₃R¹, hydroxyl, cyano,C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, aryl and/or a 5- to 7-memberedheterocyclic radical which is bonded via a nitrogen atom and may containfurther heteroatoms and be aromatic, in the presence of an aproticorganic solvent, of a palladium complex as a catalyst, of a copper saltas a cocatalyst and of a base to give the rylene dye of the formula I″which is substituted in the rylene core and where R′ is —C≡C—R″ and mdoes not equal 0, or d4) by reacting with ammonia or an amine of thegeneral formula VI

in the presence of a dipolar aprotic organic solvent to give the rylenedye of the formula I″ which is substituted in the rylene core and whereR′ is —NR³ ₂ and m does not equal
 0. 5. A process for preparingnonsymmetrical rylene dyes of the general formula I′″

where the variables are defined as follows: R is hydrogen; C₁-C₃₀-alkylwhose carbon chain may be interrupted by one or more —O—, —S—, —NR¹—,—CO— and/or —SO₂— moieties and may be mono- or polysubstituted bycarboxyl, sulfo, hydroxyl, cyano, C₁-C₆-alkoxy and/or a 5- to 7-memberedheterocyclic radical which is bonded via a nitrogen atom and may containfurther heteroatoms and be aromatic; C₅-C₈-cycloalkyl whose carbonframework may be interrupted by one or more —O—, —S— and/or —NR¹—moieties and may be mono- or polysubstituted by C₁-C₆-alkyl; aryl orhetaryl which may each be mono- or polysubstituted by C₁-C₁₈-alkyl,C₁-C₆-alkoxy, halogen, hydroxyl, cyano, carboxyl, —CONHR², —NHCOR²and/or aryl- or hetarylazo, each of which may be substituted byC₁-C₁₀-alkyl, C₁-C₆-alkoxy, halogen, hydroxyl, cyano and/or carboxyl; R′is bromine; cyano; —NR³ ₂; aryloxy, arylthio, hetaryloxy or hetarylthio,each of which may be mono- or polysubstituted by C₁-C₁₂-alkyl,C₁-C₁₂-alkoxy, cyano, —CONHR² and/or —NHCOR²; C₃-C₁₈-alk-1-ynyl whosecarbon chain may be interrupted by one or more —O—, —S—, —NR¹—, —CO—and/or —SO₂— moieties and may be mono- or polysubstituted by —COOR¹,—SO₃R¹, hydroxyl, cyano, C₁-C₆-alkoxy, C₅-C₈-cycloalkyl, aryl and/or a5- to 7-membered heterocyclic radical which is bonded via a nitrogenatom and may contain further heteroatoms and be aromatic; R¹ is hydrogenor C₁-C₆-alkyl; R² is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each ofwhich may be substituted by C₁-C₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyland/or cyano; R³ is hydrogen; C₁-C₁₈-alkyl; aryl or hetaryl, each ofwhich may be substituted by C₁-C₈-alkyl, C₁-C₆-alkoxy, halogen, hydroxyland/or cyano; both R³ radicals may be joined to give a 5- to 7-memberedheterocyclic radical which contains the nitrogen atom and is bonded viait; n, n′ are each 1,2,3 or 4,and n≠n′; m is from 0 to 6, whichcomprises a1) initially reacting a rylene derivative monobrominated inthe peri-position of the general formula II′

with excess 1,5-diaminoanthraquinone in a first cross-coupling reactionin the presence of an aprotic organic solvent, of a transition metalcatalyst system and of a base, a2) reacting the amin orylenanthramineobtained in step a) of the general formula IIIa

with a rylene derivative monobrominated in the peri-position of thegeneral formula II″

in the presence of an aprotic organic solvent, of a transition metalcatalyst and of a base in a second cross-coupling reaction, b) cyclizingthe rylenanthramine formed in step a) of the general formula III′″

in the presence of a polar organic solvent and of a base to give therylene dye of the formula I′″ which is unsubstituted in the rylene coreand where m is 0, and c) if desired, converting the rylene dye I′″unsubstituted in the rylene core and obtained in step b) to the rylenedye of the formula I′″ brominated in the rylene core where R′ is bromineand m does not equal 0 by reacting with elemental bromine, and d) ifdesired, converting the rylene dye I′″ brominated in the rylene core andobtained in step c) d1) by reacting with a compound of the generalformula IV

where Z is sulfur or oxygen and the ring A is an aryl or hetarylradical, each of which may be mono- or polysubstituted by C₁-C₁₂-alkyl,C₁-C₁₂-alkoxy, cyano, —CONHR² and/or —NHCOR², in the presence of aninert nitrogen-basic organic solvent and of a base to give the rylenedye of the formula I′″ which is substituted in the rylene core and whereR′ is aryloxy, arylthio, hetaryloxy or hetarylthio, each of which may bemono- or polysubstituted by C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy, cyano, —CONHR²and/or —NHCOR², and m does not equal 0, d2) by reacting with copper(I)cyanide in the presence of a dipolar aprotic organic solvent to give therylene dye of the formula I′″ which is substituted in the rylene coreand where R′ is cyano and m does not equal 0, d3) by reacting with analkyne of the general formula VH—C≡C—R″  V where R″ is a C₁-C₁₆-alkyl radical which may be interruptedby one or more —O—, —S—, —NR¹—, —CO— and/or —SO₂— moieties and may bemono or polysubtituted by —COOR¹, —SO₃R¹, hydroxyl, cyano, C₁-C₆-alkoxy,C₅-C₈-cycloalkyl, aryl and/or a 5- to 7-membered heterocyclic radicalwhich is bonded via a nitrogen atom and may contain further heteroatomsand be aromatic, in the presence of an aprotic organic solvent, of apalladium complex as a catalyst, of a copper salt as a cocatalyst and ofa base to give the rylene dye of the formula I′″ which is substituted inthe rylene core and where R′ is —C≡C—R″ and m does not equal 0, or d4)by reacting with ammonia or an amine of the general formula VI

in the presence of a dipolar aprotic organic solvent to give the rylenedye of the formula I′″ which is substituted in the rylene core and whereR′ is —NR³ ₂ and m does not equal
 0. 6. A method for coloring highmolecular weight organic and inorganic materials comprising utilizingthe rylene dye as claimed in claim
 1. 7. The method as claimed in claim6 wherein said high molecular weight organic and inorganic materials areplastics, paints, printing inks and oxidic layer systems.
 8. Adispersant, a pigment additive for organic pigments and an intermediatefor the preparation of pigment additives comprising the rylene dye asclaimed in claim
 1. 9. A method for producing an aqueous polymerdispersion which is colored or absorbs in the near infrared region ofthe electromagnetic spectrum comprising adding the rylene dye as claimedin claim 1 to the aqueous polymer dispersion.
 10. A photoconductor inelectrophotography comprising the rylene dye as claimed in claim
 1. 11.A plastic, a paint, a printing ink, and an oxidic layer systemcomprising the rylene dye as claimed in claim
 1. 12. An aqueous polymerdispersion comprising the rylene dye as claimed in claim 1.